OCCURRENCE OF ESTERS

ESTERS • # of esters is very large.

Friday, November 27, 2020 06:11 PM • both natural and synthesized esters exist in almost endless variety.

ESTERS PHYSICAL PROPERTIES

• responsible for the sweet and pleasant odors and tastes of our food • Cannot form hydrogen bonds to each other
○ We use these compounds as artificial flavors in foods in place of more expensive natural • BP is lower than those of alcohols and acids of comparable mass
extracts • More like ethers in properties.
• In biochemistry, esterlike molecules act as the energy carriers in many cells • Low molecular mass esters are soluble in water.
• Carboxylic derivatives • ↓Solubility ↑carbon chain length

Formula: RCOOR’ ○ Simple esters

○ R and R’ are hydrocarbon groups. ▪ derived from monocarboxylic acids and monohydroxy alcohols
▪ R(1) may be ▪ Colorless
□ hydrogen, an alkyl group, or an aryl group ▪ liquids or solids.
▪ R(2) may be ▪ generally nonpolar/low polarity
□ alkyl group or an aryl group, but not a hydrogen □ Because their water solubility and boiling points are lower than those of either
○ derived from a carboxylic acid and an alcohol in which the OH of the acid is replaced by an acids or alcohols of similar molar masses.
OR group
○ looks somewhat like an ether & a carboxylic acid. ○ Low- and intermediate-molar-mass esters
▪ But compounds in this group react neither like carboxylic acids/ethers ▪ from both acids and alcohols up to about 10 carbons
□ Unlike ethers, esters have a carbonyl group. ▪ liquids
□ Unlike carboxylic acids, esters have no acidic hydrogen atom; they have a ▪ characteristic (usually fragrant or fruity) odors.
hydrocarbon □ Causes the distinctive odor and flavor of many fruits

○ High-molar-mass esters
• formed from acids and alcohols of 16 or more carbons
• waxes (physical state)
○ used in furniture wax and automobile wax preparations
e.g. carnauba wax contains esters of
• found throughout nature. ▪ 24- and 28-carbon fatty acids
○ ester linkage ▪ 32- and 34-carbon alcohols.
• Polyesters with very high molar masses
▪ Particularly important in the study of fats and oils (both esters)
○ Esters of phosphoric acid ○ widely used in the textile industries.
▪ vital to life e.g. Dacron
• obtained from various plants
NOMENCLATURE
○ alcohol derivatives of carboxylic acids. The difference in properties of an acid vs esters
○ named in much the same way as salts. • butyric acid has an extremely unpleasant odor
alcohol part + acid (suffix: ic → -ate) • ethyl butyrate has the pleasant odor of pineapple
□ RC=O comes from the acid • methyl butyrate the odor of rum.
□ R'O comes from the alcohol
IUPAC: ○ Flavoring and scenting agents.
methyl ethanoate ○ generally good solvents for organic substances
• ethyl acetate, butyl acetate, and isoamyl acetate
○ used extensively in paints, varnishes, and lacquers.
COMMON:
methyl acetate ○ Bc low molar masses are volatile

CHEMICAL PROPERTIES
COMPOUND COMMON IUPAC • majority of organic and biochemical substances react only very slowly with water.
HCOOCH3 methyl formate methyl methanoate • to increase the rate of these reactions, a catalyst is required.
CH3COOCH3 methyl acetate methyl ethanoate ○ In lab, acid/base act as a catalyst for hydrolysis.
○ In living systems/body, enzymes (aldehydes, ketones, biomolecules)act as catalysts
CH3COOCH2CH3 ethyl acetate ethyl ethanoate
• Esters are neutral compounds
CH3CH2COOCH2CH3 ethyl propionate ethyl propanoate ○ unlike the acids
CH3CH2CH2COOCH(CH3)2 isopropyl butyrate isopropyl butanoate ○ In typical reactions, the alkoxy (OR′) group of an ester is replaced by another group
• e.g. hydrolysis

Hydrolysis of Esters
• literally “splitting with water.”
• most important reaction of esters
ethyl benzoate ethyl benzoate • the splitting of molecules through the addition of water
• catalyzed by either an acid or a base.

Acidic hydrolysis
○ reverse of esterification.
Methyl propionate Methyl propanoate ○ ester is heated with a large excess of water containing a strong -acid catalyst
• reaction with water to form a carboxylic acid and an alcohol
○ water (HOH) splits the ester bond.
• H of HOH joins to the oxygen atom in the OR part of the original ester
propyl formate propyl • OH of HOH joins to the carbonyl carbon atom:
methanoate

▪ Products: butyric acid (butanoic acid) and ethanol.

butyl propionate butyl propanoate
○ Like esterification, the reaction is reversible and does not go to completion.
○ catalyzed by strong acids (H 2SO4 and HCl) or by certain enzymes:

ethyl pentanoate.

Esters of aromatic acids

○ named in the same general way as those of aliphatic acids

Ethyl benzoate. Alkaline Hydrolysis (Saponification)

Saponification

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 Ethyl benzoate. Alkaline Hydrolysis (Saponification)
Saponification
○ From Latin
Diesters • Sapon = “soap”
• Facere = “to make”
○ Called as such because soaps are prepared by the alkaline hydrolysis of fats
and oils
○ hydrolysis of an ester by a strong base (NaOH or KOH) = alcohol and a salt
(or soap if the salt formed is
diethyl malonate
from a high-molar-mass acid)
Selected Common Esters
ESTER IUPAC COMMON ODOR/FLAVOR
CH3COO(CH2)4 CH3 Pentyl ethanoate Banana
CH3CH2COO(CH2)4CH3 Pentyl propanoate Apricot
CH3(CH2)2COOCH3 Methyl butanoate Apple
HCOOCH2CH(CH3)2 isobutyl methanoate Isobutyl formate Raspberry

○ The carboxylic acid may be obtained by reacting the salt with a strong acid:

CH3COO(CH2)7 CH3 Octyl ethanoate Octyl acetate Orange

○ Base (NaOH or KOH)
• reactant, not a catalyst
○ reaction goes to completion
CH3(CH2)2COOCH2CH3 Ethyl butanoate Ethyl butyrate pineapple ○ Water is the catalyst
• used to hydrolyze an ester
○ products are a carboxylate salt and an alcohol.

e.g. ethyl acetate + NaOH = sodium acetate and ethanol:

Methyl 2-hydroxybenzoate Methyl salicylate Wintergreen

Methyl-2-aminobenzoate Grape Significance

○ allows esters to fill an important surgical need.
• After a surgeon makes an internal incision, he/she closes the cut with stitches
○ almost always, must dissolve as the cut heals.
○ Originally, formed from thread made of animal intestines (“catgut”) that could
be degraded by enzymes.
Isopentyl ethanoate Isoamyl acetate Banana, pear ○ Today, almost all dissolvable sutures are made from special polyesters.
▪ formed using the hydroxy acids glycolic acid & lactic acid

LESSON 12/4/20 ENDED HERE

Polyesters: Condensation Polymers
Condensation polymers
• formed by substitution reactions between neighboring monomers. ▪ hydroxyl group of monomer (1) + carboxylic acid monomer(2)
• The polyesters are joined by ester linkages between carboxylic acid and alcohol groups ◊ form an ester and to continue growth of the polymer.
○ macromolecule formed may be linear or cross-linked.  The finished polymer is a chain of esters (a polyester).
Linear polyester ◊ When the esters hydrolyze, the chain is broken and the stitches
○ obtained from the bifunctional monomers terephthalic acid (diacid) and ethylene glycol. dissolve.
Esterification ◊ Since this is a synthetic polymer, the properties of the suturing
○ occurs between the alcohol and acid groups on both ends of both monomers material can be varied, allowing the surgeon to choose different
▪ forming long-chain macromolecules thicknesses (and strengths), different elasticities, and different
dissolving rates.
◊ A simple organic reaction makes this high-tech medicine possible—
ester hydrolysis.

• may be drawn into fibers or formed into transparent films of great strength.

made from this polyester

• Dacron and Terylene synthetic textiles and Mylar films
• 2-L soft-drink bottle.

The symbol on objects made of this material is shown in the margin.

In actual practice, the dimethyl ester of terephthalic acid is used as the monomer, and the molecule
split out is methyl alcohol instead of water.
When trifunctional acids or alcohols are used as monomers, cross -linked thermosetting polyesters are
obtained.
• e.g. reaction of glycerol and o-phthalic acid.
The polymer formed is one of a group of polymers known as alkyd resins.
Glycerol has three functional -OH groups, and phthalic acid has two functional COOH groups:

A cross-linked macromolecular structure is formed that, with modifications, has proved

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A cross-linked macromolecular structure is formed that, with modifications, has proved
to be one of the most outstanding materials used in the coatings industry.

PREPARATION OF ESTERS
a. Esterification
○ carboxylic acid + alcohol
○ heated in the presence of a mineral acid catalyst
○ products: ester and water

○ reaction is reversible.
e.g. acetic acid + 1-butanol = butyl acetate

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